Synthesis, electrochemistry, in-situ spectroelectrochemistry and molecular structures of 1,4-naphthoquinone derivatives

Article abstract of DOI:10.1016/j.molstruc.2020.129145

A novel series of 1,4-naphthoquinones substituted containing sulfur, nitrogen, oxygen atoms were synthesized. The structures of the novel products were characterized by using the various spectroscopic techniques such as ¹H nuclear magnetic resonance (NMR), ¹³C NMR, mass spectrometry (MS), Fourier transform infrared spectroscopy (FT-IR) and microanalysis. The crystal structures of 2,3-bis(benzylsulfanyl)-1,4-napthoquinone 4 and 2,3-bis(ethylsulfanyl)-1,4-naphthoquinone 7 were determined by using X-ray single crystal diffraction method. Electrochemical behaviors of some 1,4-naphthoquinone (NQ) derivatives 3, 4, 7, 8, 9, 10, 12, 13, 15, 16, 17, 19 and 20 were studied by using cyclic voltammetry, square wave voltammetry and in-situ UV-Vis spectroelectrochemistry. The substituents of the NQ derivatives significantly altered the redox mechanism. In-situ UV-Vis spectroelectrochemical analyses of NQs supported the proposed redox mechanism.

Full text of DOI:10.1016/j.molstruc.2020.129145

Journal of Molecular Structure 1224 (2021) 129145
Contents lists available at ScienceDirect
Journal of Molecular Structure
journal homepage: www.elsevier.com/locate/molstr
Synthesis, electrochemistry, in-situ spectroelectrochemistry and
molecular structures of 1,4-naphthoquinone derivatives
a,∗
a
b
c
Nahide Gulsah Deniz , Cigdem Sayil , Duygu Akyüz , Atif Koca
a
Division of Organic Chemistry, Department of Chemistry, Engineering Faculty, Istanbul University-Cerrahpasa, 34320, Avcilar, Istanbul, Turkey
Department of Chemistry, Faculty of Science, Gebze Technical University, 41400, Gebze, Kocaeli, Turkey
b
c
Department of Chemical Engineering, Engineering Faculty, Marmara University, 34722, Goztepe, Istanbul, Turkey
a r t i c l e i n f o
a b s t r a c t
Article history:
A novel series of 1,4-naphthoquinones substituted containing sulfur, nitrogen, oxygen atoms were synthe-
Received 18 May 2020
Revised 19 August 2020
Accepted 24 August 2020
Available online 25 August 2020
sized. The structures of the novel products were characterized by using the various spectroscopic tech-
niques such as 1H nuclear magnetic resonance (NMR), 13 C NMR, mass spectrometry (MS), Fourier trans-
form infrared spectroscopy (FT-IR) and microanalysis. The crystal structures of 2,3-bis(benzylsulfanyl)-1,4-
napthoquinone 4 and 2,3-bis(ethylsulfanyl)-1,4-naphthoquinone 7 were determined by using X-ray single
crystal diffraction method. Electrochemical behaviors of some 1,4-naphthoquinone (NQ) derivatives 3, 4,
7, 8, 9, 10, 12, 13, 15, 16, 17, 19 and 20 were studied by using cyclic voltammetry, square wave voltamme-
try and in-situ UV-Vis spectroelectrochemistry. The substituents of the NQ derivatives significantly altered
the redox mechanism. In-situ UV-Vis spectroelectrochemical analyses of NQs supported the proposed re-
dox mechanism.
Keywords:
Naphthoquinones
Spectroelectrochemistry
Electrochemical behaviors
Cyclic voltammetry
in-situ UV-Vis spectroelectrochemistry
Crystal structure
© 2020 Elsevier B.V. All rights reserved.
1. Introduction
Because of their biological importance, the redox reactions of
the 1,4-naphthoquinone derivatives have been investigated to their
Naphthoquinone derivatives occur naturally as plant con-
stituents, and many of these have found use as colorant in
the past. The color of the naphthoquinone compounds can be
produced in the 1,4-naphthoquinone chromogen by introducing
amino and hydroxyl groups into the quinoid ring, into the ben-
zenoid ring, or into both rings. The advantage of the naphtho-
quinone dyes is their strong and stable coloring ability [1], so
they are extensively used in the cosmetics industry in the produc-
tion of cosmetic dyes, especially hair dyes. Heterocyclic naphtho-
quinone derivatives have been gaining importance in the manu-
facturing of dyes and pigments because of their substantivity to
cellulosic and hydrophobic fibers [2]. Moreover, particularly 1,4-
naphthoquinones are widely distributed phenolic compounds in
nature such as naphthoquinones are reported to exhibit diverse
pharmacological properties like antibacterial [3], antifungal, antivi-
ral, anti-inflammatory antipyretic and anticancer activity [4]. These
usage in various biological and electrochemical fields such as cor-
rosion inhibitor, antimicrobials and sensors [6–9]. Thus, it becomes
necessary to understand the factors which regulate the potentials
and reaction pathways of these 1,4-naphthoquinone species. While
the quinone derivatives undergo a two-step reduction with two-
step hydrogenation in aqueous media, they are first reduced to its
radical anion and then to the dianion in aprotic solvents. While
the ideal reduction reactions are the two identical reduction cou-
ples with similar peak currents and peak to peak separation, sub-
stituent environments of the quinone derivatives frequently cause
deviation significantly from those expected for a simple two-step
reaction [10–16]. It has been observed that most of their activities
are associated with their redox behavior. Thus, electrochemical ex-
aminations of synthesized 1,4-naphthoquinone derivatives (3, 4, 7,
8, 9, 10, 12, 13, 15, 16, 17, 19, 20) were carried out in this study in
order to use these moieties for the practical applications in elec-
trochemical technologies in the future.
1,4-naphthoquinones have the ability to induce oxidative stress
which is responsible for initiation of tissue damage selectively in
tumor cells and this seems to be a promising approach for target-
ing cancer cells [5].
2. Materials and methods
2
.1. Experimental section
∗
Melting points were measured on a Buchi B-540 melting point
Correspondence author.
E-mail address: yurdakul@istanbul.edu.tr (N.G. Deniz).
apparatus. TLC plates silica 60F254 (Merck, Darmstadt), detection
https://doi.org/10.1016/j.molstruc.2020.129145
0
022-2860/© 2020 Elsevier B.V. All rights reserved.

2
N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
Scheme 1. The synthesis of S,S- and S,O-substituted-1,4-naphthoquinones in the presence of ethanol.
Scheme 2. The synthesis of S-, S,S-, N- and N,S-substituted-1,4-naphthoquinones in the presence of DMF or chloroform.
with ultraviolet light (254 nm). Elemental analyses were performed
on a Thermo Finnigan Flash EA 1112 Elemental analyzer. Infrared
2.2. Synthesis procedures
(
IR) spectra were recorded in KBr pellets in Nujol mulls on a
The heteroatom substituted-1,4-naphthoquinone compounds 3,
4 [21], 7 [21], 8, 9 [16], 10 [16], 12 [22], 13, 15, 16, 17, 19 [23] and
20 were synthesized acourding to method 1, 2, 3 and illustrated in
Schemes 1, 2 and 3. The synthesized 1,4-naphthoquinone deriva-
tives 3, 8, 13, 15, 16, 17 and 20 were fully new compounds. All
spectroscopic data ( H NMR, 13C NMR, FTIR, MS) and results of
micro analysis were given in the experimental section for charac-
terization of these new 1,4-naphthoquinone compounds 3, 8, 13,
15, 16, 17 and 20. In addition to, some known 1,4-naphthoquinone
compounds (4, 7, 9, 10, 12, 19) were yielded from these reac-
tions. The synthesis method and spectral characterizations of these
Perkin Elmer Precisely Spectrum One FTIR spectrometry. 1H and
13C NMR spectra were recorded on Varian UNITYINOVA operat-
ing at 500 MHz. Mass spectra were obtained on a Thermo Finni-
gan LCQ Advantage MAX LC/MS/MS spectrometer according to ESI
probe. Products were isolated by column chromatography on Sil-
ica gel (Fluka Silica gel 60, particle size 63-200 μm). All chemicals
were reagent grade and used without further purification. Moisture
was excluded from the glass apparatus using CaCl2 drying tubes.
Solvents, unless otherwise specified, were of reagent grade and dis-
tilled once prior to use.
1

N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
3
known quinone compounds 4, 7, 9, 10, 12 and 19 were previously
reported in the related literature [16,21–23]. The both study of
crystal structure determination of compounds 4, 7 and their elec-
trochemical properties of compounds (4, 7, 9, 10, 12, 19) were
firstly investigated in this study. The electrochemical properties of
all synthesized compounds were investigated in this study.
Yield: 0.57 g (45%); Red oil; Rf = 0.40 (CHCl ); FT-IR (KBr pellet,
3
cm 1): 3071 (CHarom), 2968, 2927, 2874 (C-H), 1663 (C=O), 1593
−
1
(C=C); H NMR (499.74 MHz, CDCl ): δ = 0.9 (t, J = 8.34 Hz,
3
3H, CH ), 1.1 (t, J = 7.32 Hz, 3H, CH ), 1.4 (d, 3H, CH ), 1.45-1.6
3
3
3
(m, 2H, CH ), 3.8 (m, 1H, S-CH), 4.4-4.5 (q, 2H, O-CH ), 7.55 (t,
2
2
J = 7.32 Hz, 1H, Harom), 7.65 (d, 1H, Harom), 7.95 (dd, J = 7.81 Hz,
J = 6.35 Hz, 1H, Harom), 8.0 ppm (dd, J = 6.84 Hz, J = 5.32 Hz,
Method 1: Sodium carbonate (1.52 g) was dissolved (60 mL)
in ethanol. 2,3-Dichloro-1,4-naphthoquinone 1 and nucle-
ophiles 2 or (5, 6) or 11 or (6, 14) were added slowly to
this solution. Without heating, the mixture was stirred for
1
H, Harom); 13C NMR (125.66 MHz, CDCl ): δ = 14.93, 14.99, 17.35
3
(
CH ), 20.02 (CH ), 29.34 (S-CH), 68.92 (-OCH ), 125.80, 125.87,
3 2 2
1
31.37, 132.47, 132.60, 132.85 (CHarom, Carom), 133.23 (=C-S), 157.53
+
(
=C-O), 178.68, 181.86 ppm (C=O); MS [+ESI]: m/z 290 [M] ,
O S (M = 290.383 g/mol). Calculated: C, 66.18; H, 6.24; S,
6
hours. The color of the solution quickly changed and the
extent of the reaction was monitored by TLC. Chloroform
30 mL) was added to the reaction mixture. The organic
C
H
18
16
3 1
1
1.04%. Found: C, 66.19; H, 6.25; S, 11.04%.
-(Butylsulfanyl)-3-etoxy-1,4-naphthoquinone (15):
Compound 15 was synthesized from reaction of 1 (1.0 g, 4.40
(
2
layer was washed with water (4 × 30 mL), and dried with
Na2SO4. After the solvent was evaporated the residue was
purified by column chromatography on silica gel.
mmol) with 6 (0.84 g, 4.40 mmol) and 14 (0.39 g, 4.40 mmol) ac-
cording to the method 1. Yield: 0.47 g (37%); Red oil; Rf = 0.40
Method 2: 2,3-Dichloro-1,4-naphthoquinone 1 and nucleophile
compound 6 in the presence of dimethylformamide (DMF)
(
(
CHCl ); FT-IR (KBr pellet, cm 1): 3071 (CHarom), 2959, 2929, 2872
−
3
1
C-H), 1662 (C=O), 1593 (C=C); H NMR (499.74 MHz, CDCl ):
(
50 mL) were stirred and heated at 60°C for 6 hours. The
3
δ = 0.95 (t, J = 8.34 Hz, 3H, CH ), 1.2 (t, J = 7.32 Hz, 3H, CH ),
extent of the reaction was monitored by Thin-Layer Chro-
matography (TLC). Chloroform (30 mL) was added to the re-
action mixture. The organic layer was washed with water
3
3
1
.4 (m, 2H, 6.84 Hz, 1H, Harom), 7.60 (d, 1H, Harom), 7.68 (dd,
J = 7.81 Hz, J = 6.85 Hz, 1H, Harom), 7.95 (dd, J = 6.84 Hz, J = 5.32
Hz, 1H, Harom), 8.2 (dd, J = 5.84 Hz, J = 6.84 Hz, 1H, Harom);
(
4 × 30 mL) and dried with Na2SO4. After the solvent was
1
3
C NMR (125.66 MHz, CDCl ): δ = 14.88, 15.00 (CH ), 20.84,
evaporated the residue was purified by column chromatog-
raphy on silica gel.
3
3
2
8.67 (CH ), 31.26 (S-CH ), 68.89 (-OCH ), 125.36, 125.57, 125.85,
2 2 2
1
25.95, 132.50, 132.56 (CHarom, Carom), 133.26 (=C-S), 156.77 (=C-
Method 3: 2,3-Dichloro-1,4-naphthoquinone 1 and nucleophiles
+
O), 177.90, 181.89 ppm (C=O); MS [+ESI]: m/z 290 [M] , 275 [M-
6
and 18 in the presence of chloroform (50 mL) were stirred
+
(
CH )] ; C
H
16 18
O S (M = 290.383 g/mol). Calculated: C, 66.18; H,
3 1
without heating for 8 hours. The extent of the reaction was
monitored by TLC. Chloroform (30 mL) was added to the re-
action mixture. The organic layer was washed with water
3
6
.24; S, 11.04%. Found: C, 66.17; H, 6.25; S, 11.05%.
-(Butylsulfanyl)-3-(7-sulphanyl-4-methyl-coumarinyl)-1,4-
2
naphthoquinone (16):
(
4 × 30 mL) and dried with Na2SO4. After the solvent was
Compound 16 was synthesized from reaction of 1 (1.0 g, 4.40
mmol) with 6 (0.84 g, 4.40 mmol) and 14 (0.39 g, 4.40 mmol) ac-
evaporated the residue was purified by column chromatog-
raphy on silica gel.
cording to the method 1. Yield: 0.48 g (25%); Black oil; R = 0.50
f
2
-Benzylsulfanyl-3-ethoxy-1,4-naphthoquinone (3):
−1
(
(
CHCl ); FT-IR (KBr pellet, cm ): 3062 (CHarom), 2959, 2928, 2871
3
Compound 3 was synthesized from reaction of 1 (1.0 g, 4.40
mmol) with 2 (0.54 g, 4.40 mmol) according to the method 1.
1
C-H), 1621 (C=O), 1600 (C=C); H NMR (499.74 MHz, CDCl ):
3
δ = 0.84 (t, J = 8.34 Hz, 3H, CH ), 1.3-1.4 (m, 2H, CH ), 1.6
3
2
Yield: 0.78 g (52%); Red oil; Rf = 0.40 (CHCl ); FT-IR (KBr pel-
3
(
m, 2H, S-CH -CH ), 2.3 (s, 3H, CH ), 3.3 (t, J = 7.32 Hz, 2H, S-
2
2
3
let, cm 1): 3063 (CHarom), 2923, 2852 (C-H), 1661 (C=O), 1600
−
13
CH ), 6.1 (s, 1H, CH), 7.1-8.1 (m, 7H, Harom);
C NMR (125.66
2
1
(
C=C); H NMR (499.74 MHz, CDCl ): δ = 1.18 (t, J = 6.84 Hz, 3H,
3
MHz, CDCl ): δ = 12.57, 17.58 (CH ), 20.81 (CH ), 31.45 (S-CH -
3
3
2
2
CH ), 4.4 (q, 2H, O-CH ), 6.1 (s, 2H, S-CH -Ph), 7.0-8.2 ppm (m, 9H,
3
2
2
CH ), 34.0 (S-CH ), 113.69 (CH), 115.83, 117.56, 123.75, 123.99,
2
2
Harom); 13C NMR (125.66 MHz, CDCl ): δ = 12.41 (CH ), 28.67 (S-
3
3
126.24, 131.38, 131.99, 132.72, 133.11, 138.54, 139.08 (CHarom,
CH ), 65.17 (-OCH ), 113.91, 117.70, 123.93, 126.19, 126.29, 127.70,
2
2
Carom), 150.95, 152.63 (=C-S), 159.27 (C=O), 176.30, 178.75 ppm
1
31.94, 132.81, 133.07, 135.88 (CHarom, Carom), 138.42 (=C-S), 153.07
+
(
C=O); MS [+ESI]: m/z 437 [M] . C
H
O S (M = 436.54 g/mol).
4 2
24
20
+
(
=C-O), 176.39, 178.69 ppm (C=O); MS [+ESI]: m/z 348 [M+Na] ;
Calculated: C, 66.03; H, 4.62; S, 14.69%. Found: C, 66.04; H, 4.65;
S, 14.65%.
C
9
H
O S (M = 324.402 g/mol). Calculated: C, 70.34; H, 4.97; S,
3 1
1
9
16
.88%. Found: C, 70.33; H, 4.95; S, 9.89%.
-Etylsulfanyl-3-ethoxy-1,4-naphthoquinone (8):
Compound 8 was synthesized from reaction of 1 (1.0 g, 4.40
2-(7-Sulphanyl-4-methyl-coumarinyl)-3-chloro-1,4-
2
naphthoquinone (17):
Compound 17 was synthesized from reaction of 1 (1.0 g, 4.40
mmol) with 6 (0.84 g, 4.40 mmol) according to the method 2.
Yield: 0.72 g (43%); Orange oil; R = 0.50 (CHCl ); FT-IR (KBr pel-
mmol) with 5 (0.27 g, 4.40 mmol) and 6 (0.84 g, 4.40 mmol) ac-
cording to the method 1. Yield: 0.47 g (41%); Red oil; Rf = 0.50
f
3
−
(
(
CHCl ); FT-IR (KBr pellet, cm 1): 3071 (CHarom), 2975, 2927, 2869
−1
1
3
let, cm ): 3019 (CHarom), 2400 (C-H), 1670 (C=O), 1600 (C=C);
H
1
C-H), 1659 (C=O), 1591 (C=C); H NMR (499.74 MHz, CDCl ):
3
NMR (499.74 MHz, CDCl ): δ = 2.3 (s, CH ), 6.2 (s, 1H, CH), 7.1-8.2
3
3
δ = 1.2 (t, J = 8.34 Hz, 3H, CH ), 1.4 (t, J = 7.32 Hz, 3H, CH ),
13
3
3
(
m, 7H, Harom); C NMR (125.66 MHz, CDCl ): δ = 17.60 (CH ),
3
3
3
.2 (q, 2H, S-CH ), 4.4 (q, 2H, O-CH ), 7.65 (t, J = 7.32 Hz, 1H,
2
2
1
14.46 (CH), 117.98 (=C-CH ), 118.57, 124.11, 125.54, 126.64, 126.71,
3
Harom), 7.55 (d, 1H, Harom), 7.92 (dd, J = 7.81 Hz, J = 6.35 Hz,
1
30.18, 131.10, 133.45, 133.49, 136.09, 144.17 (CHarom, Carom), 144.72
1
1
H, Harom), 7.95 ppm (dd, J = 6.84 Hz, J = 5.32 Hz, 1H, Harom);
C NMR (125.66 MHz, CDCl ): δ = 14.25, 14.87 (CH ), 28.67 (S-
(
=C-S), 150.69 (S-C=), 152.53 (=C-Cl), 159.03 (=C-O), 174.62,
3
3
3
+
1
77.35 ppm (C=O); MS [+ESI]: m/z 383 [M] , MS/MS [+ESI]: m/z
CH ), 68.91 (-OCH ), 125.38, 125.71, 130.46, 131.37, 132.52, 132.58
+
2
2
3
47 [M-Cl]+, 319 [M-(Cl+CH+CH )] ; C
H
20 11
O S Cl (M = 382.77
3
4
1
1
(
(
(
CHarom, Carom), 133.42 (=C-S), 156.72 (=C-O), 177.91, 181.91 ppm
g/mol). Calculated: C, 62.75; H, 2.89; S, 8.37%. Found: C, 62.73; H,
+
+
C=O); MS [+ESI]: m/z 262 [M] , 235 [M-(CH -CH )] ; C
H O S
14 14 3 1
2
3
5
.85; S, 8.35%.
-Morpholinyl-3-(7-sulphanyl-4-methyl-coumarinyl)-1,4-
M = 262.332 g/mol). Calculated: C, 61.10; H, 5.37; S, 12.22%.
2
Found: C, 61.03; H, 5.35; S, 12.25%.
-(Isopropylsulfanyl)-3-etoxy-1,4-naphthoquinone (13):
naphthoquinone (20):
2
Compound 20 was synthesized from reaction of 1 (1.0 g, 4.40
mmol) with 6 (0.84 g, 4.40 mmol) and 18 (0.84 g, 4.40 mmol) ac-
Compound 13 was synthesized from reaction of 1 (1.0 g, 4.40
mmol) with 11 (0.39 g, 4.40 mmol) according to the method 1.

4
N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
Table 1
Voltammetric data of the NQ derivatives.
NQ/NQ.- reduction couple
.−
NQ /NQ2- reduction couple
NQ2 /NQ22- reduction couple
.−
Compounds
aE1/2 vs. SCE (V)
bꢀ Ep
Ipa/Ipc
aE1/2 vs. SCE (V)
bꢀ Ep
Ipa/Ipc
aE1/2 vs. SCE (V)
bꢀ Ep
Ipa/Ipc
3
4
7
8
9
-0.42
-0.43
-0.46
-0.48
-0.42
-0.22
-0.47
-0.45
-0.42
-0.33
-0.20
-0.58
-0.53
70
67
62
69
63
67
85
85
67
64
63
87
76
0.98
1.00
0.97
0.92
0.93
0.90
0.98
0.92
0.90
0.86
0.98
0.90
0.89
-0.96
-1.06
-1.08
-1.12
-1.06
-0.78
-1.16
-1.15
-1.35
-0.96
-0.78
-1.08
-1.30
75
64
60
65
61
65
70
82
64
61
64
68
67
0.96
0.97
0.95
0.93
0.96
0.92
0.97
0.90
0.92
0.42
0.96
0.88
0.93
-
-
-
-1.90
-1.87
-
-
-
-
1
1
1
1
1
1
1
2
0
2
3
5
6
7
9
0
-1.93
-1.93
-1.82
-1.88
-1.85
-
-
-
-
100
0.34
-
-
-
-
a
E1/2 values were given for reversible processes. Epc values were given for irreversible reduction processes.
b
ꢀEp = | Epa- Epc|.
cording to the method 3. Yield: 0.72 g (38%); Red oil; Rf = 0.40
−
(
(
CHCl ); FT-IR (KBr pellet, cm 1): 3014 (CHarom), 2963, 2922, 2862
3
1
C-H), 1621 (C=O), 1600 (C=C); H NMR (499.74 MHz, CDCl ):
3
δ = 2.3 (s, CH ), 3.5, 3.7 (t, J = 9.27 Hz, J = 9.27 Hz, 8H, Hmorp),
3
6
.1 (s, 1H, CH), 7.1-8.0 (m, 7H, Harom); 13C NMR (125.66 MHz,
CDCl ): δ = 17.57(CH ), 51.57, 66.41 (Cmorp), 114.24 (CH), 117.19
3
3
(
=C-CH ), 116.76, 121.50, 123.95, 124.23, 125.70, 126.05, 131.02,
3
1
31.34, 132.23, 133.36, 141.33 (CHarom, Carom), 141.33 (=C-S), 151.09
(
S-Carom), 154.77 (=C-N), 159.40 (=C-O), 177.12, 180.00 ppm (C=O);
+
MS [+ESI]: m/z 434 [M] ; C
H
O S N (M = 433.487 g/mol).
24
19
5
1
1
Calculated: C, 66.49; H, 4.41; N, 3.23; S, 7.39%. Found: C, 66.50;
H, 4.45; S, 7.35%.
2
.3. Electrochemical and spectroelectrochemical studies
Electrochemical and spectroelectrochemical measurements
were carried out with
a
Gamry Reference 600 potentio-
stat/galvanostat utilizing a three-electrode configuration at 25°C.
For cyclic voltammetry (CV), and square wave voltammetry (SWV)
measurements, the working electrode was a Pt disc with a surface
2
area of 0.071 cm . The surface of the working electrode was
polished with a diamond suspension before each run. A Pt wire
served as the counter electrode. Ag/AgCl electrode was employed
as the reference electrode and separated from the bulk of the
solution by a double bridge. Ferrocene was used as an internal
reference. Tetrabuthylammonium perchlorate (TBAP) in dimethyl-
sulfoxide (DMSO) was employed as the supporting electrolyte at
a concentration of 0.10 moldm 3. High purity N2 was used to
remove dissolved O2 at least 15 minutes prior to each run and to
maintain a nitrogen blanket during the measurements. Voltam-
metric data of the compounds were illustrated in the Table 1. IR
compensation was applied to the CV and SWV scans to minimize
the potential control error. UV/Vis absorption spectra were mea-
sured by an OceanOptics QE65000 diode array spectrophotometer.
In-situ spectroelectrochemical measurements were carried out
by utilizing a three-electrode configuration of thin-layer quartz
spectroelectrochemical cell at 25°C. The working electrode was a
semitransparent Pt tulle. A Pt wire counter electrode and a SCE
reference electrode separated from the bulk of the solution by a
double bridge were used. CV responses of compounds 4, 7, 12,
−
Fig. 1. CV responses of compound 4 at various scan rates on GCE in DMSO/TBAP.
2.4. X-ray crystallography
Red and black crystals of compounds 4 and 7 suitable for
X-ray diffraction analysis were obtained by slow evaporation of
an ethanol solution at room temperature. A red crystal of com-
pound 4, C24H18 O S , a black crystal of compound 7, C14 H14 O2S2,
2
2
having approximate dimensions of 0.30
×
0.20
×
0.10 and
0.60 × 0.30 × 0.10 mm, respectively, were mounted on a glass
fiber. All measurements were made on a Rigaku R-Axis Rapid-
S imaging plate area detector with graphite monochromatic Mo-
9, 15 and 17 at various scan rates on GCE in DMSO/TBAP were
illustrated in Figs. 1–6, respectively. UV-vis spectral changes of
˚
compounds 4, 15, 12 and 9 were given in Figs. 7–10, respectively.
Kα radiation (λ = 0.71073 A). Experimental conditions were sum-

N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
5
Fig. 2. CV responses of compound 7 at various scan rates on GCE in DMSO/TBAP.
Fig. 4. CV responses of compound 9 at various scan rates on GCE in DMSO/TBAP.
Fig. 5. CV responses of compound 15 at various scan rates on GCE in DMSO/TBAP.
Fig. 3. CV responses of compound 12 at various scan rates on GCE in DMSO/TBAP.

6
N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
Fig. 9. UV-vis spectral changes of compound 12 recorded during in-situ spectroelec-
trochemical measurements at applied potentials of a) Eapp= -0.75 V, and b) Eapp=
1.25 V in DMSO/TBAP electrolyte system. (changing of the spectrum during the re-
-
dox reactions were represented with the arrow directions).
Fig. 6. CV responses of compound 17 at various scan rates on GCE in DMSO/TBAP.
Fig. 10. UV-vis spectral changes of compound 9 recorded during in-situ spectroelec-
trochemical measurements at applied potentials of a) Eapp= -0.75 V, and b) Eapp=
-1.25 V in DMSO/TBAP electrolyte system. (changing of the spectrum during the re-
dox reactions were represented with the arrow directions).
marized in Table 2. The crystal structures were solved by SIR 92
[
17] and refined with CRYSTALS [18]. The non-hydrogen atoms
were refined anisotropically. H atoms were located in geometri-
˚
cally idealized positions C-H = 0.95(6) A and treated as riding and
iso
˚
U
(H) = 1.2Ueq(C). The selected bond distances (A), bond and tor-
sion angels (°) for compounds 4 and 7 were listed in Table 3, re-
spectively. The hydrogen bond parameters for compounds 4 and 7
were given in Table 4. Drawing was performed with the program
ORTEP-III [19] with 50% probability displacement ellipsoid. ORTEP
and unit cell packing diagrams for compounds 4 and 7 were given
in Figs. 11–15. Crystallographic data (excluding structure factors)
for the structures reported in this paper have been deposited with
the Cambridge Crystallographic Data Centre as supplementary pub-
lication numbers. CCDC-1041226, 1041225 for compounds 4 and 7,
respectively [20].
Fig. 7. UV-vis spectral changes of compound 4 recorded during in-situ spectroelec-
trochemical measurements at applied potentials of a) Eapp= -0.75 V, and b) Eapp=
1
.25 V in DMSO/TBAP electrolyte system (changing of the spectrum during the re-
dox reactions were represented with the arrow directions).
3. Result and discussion
3
.1. Chemistry
The heteroatom substituted 1,4-naphthoquninone compounds 3,
, 7, 8, 9, 10, 12, 13, 15, 16, 17, 19 and 20 were synthesized as out-
4
lined in Schemes 1 and 2. Detailed synthetic procedures (methods
-3) for all compounds are described in the experimental section.
1
All spectroscopic data ( H NMR, 13C NMR, FTIR, MS) and results
of micro analysis were given for unknown quinone derivatives 3,
8, 13, 15, 16, 17 and 20 in the experimental section. In addition
to, some known 1,4-naphthoquinone compounds (4, 7, 9, 10, 12,
1
Fig. 8. UV-vis spectral changes of compound 15 recorded during in-situ spectroelec-
trochemical measurements at applied potentials of a) Eapp= -0.75 V, and b) Eapp=
1.25 V in DMSO/TBAP electrolyte system. (changing of the spectrum during the re-
dox reactions were represented with the arrow directions).
19) were yielded from these reactions. The synthesis and spectral

N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
7
Table 2
The main crystallographic parameters of compounds 4 and 7.
Compound 4
Compound 7
Empirical formula
C24H18O2S2
C14H14O2S2
Black, prism
0.60 × 0.30 × 0.10
0.71073
Crystal colour, habit
Red, block
Crystal size (mm)
Wavelength ( A˚ )
0.30 × 0.20 × 0.10
0.71073
Crystal system
Space group
Orthorhombic
Monoclinic
P212121
Cc
a = 4.0389(3) A˚
Cell dimensions
a = 5.7143(2) A˚
b = 16.5246(5) A˚
c = 20.6520(6) A˚
b = 19.2923(9) A˚
c = 17.1209(9) A˚
Cell volume ( A˚ 3
Cell Formula units (Z)
)
1950.10(11)
1325.2(1)
4
4
Density (g.cm 3
−
)
1.371
1.395
μ [cm 1
−
]
0.290
0.392
F000
840.00
584.00
h,k,l ranges
-6≤h≤6, -19≤k≤19
-5≤h≤5, -26≤k≤26
-24≤l≤23
38346
-
24≤l≤24
Reflections collected
75388
Indepenent reflections
Data/restraints/parameters
Goodness of fit indicator
Final R indices [I>2σ(I)]
3455 [Rint = 0.081]
265/0 271
1.101
3945[Rint = 0.027]
1979 /0/ 177
1.041
R1 = 0.045
wR2 = 0.083
R1 = 0.075
wR2 = 0.096
0.56 and −0.56 e.A˚
−
3
0.67 and −0.67e.A
˚ −3
Largest diff. peak and hole
CCDC deposition number
1041226
1041225
Fig. 11. The molecular structure of compound 4. Displacement ellipsoids are plotted
at the 50% probability level.
Table 3
Selected bond distances ( A˚ ), bond and torsion
angels (°) for compounds 4 and 7.
Bond distances ( A˚ )
4
7
C2-C3
C5-C10
C1-O1
C4-O2
C2-S1
1.365(9)
1.379(9)
1.215(9)
1.222(9)
1.759(5)
1.757(5)
1.833(7)
1.828(6)
C1-C2
C8-C9
C7-O1
C10-O2
C8-S1
1.381(1)
1.352(1)
1.170(1)
1.291(1)
1.753(8)
1.729(9)
1.783(9)
1.901(1)
C3-S2
C9-S2
S1-C11
S2-C18
S1-C11
S2-C13
Bond angles (°)
4
7
C1-C2-C3
C3-C4-C5
C2-C1-C10
O1-C1-C2
O2-C4-C3
121.6(5)
C8-C9-C10
C1-C7-C8
C2-C10-C9
O1-C7-C8
O2-C10-C9
120.6(7)
117.2(6)
117.1(6)
121.9(5)
122.6(5)
116.7(8)
119.4(6)
124.8(9)
117.4(7)
Torsion angles (°)
4
7
C1-C2-C3-C4
S1-C2-C3-S2
9.6(9)
C7-C8-C9-C10
S1-C8-C9-S2
-13.0(1)
Fig. 12. The molecular structure of compound 7. Displacement ellipsoids are plot-
0.01(7)
1.0(1)
ted at the 50% probability level.
C2-S1-C11-C12
C3-S2-C18-C19
-170.2(4)
-163.8(4)
C8-S1-C11-C12
C9-S2-C13-C14
164.2(5)
156.0(1)
characterization of compounds 4, 7, 9, 10, 12 and 19 were previ-
ously reported in the related literature [16,21–23]. The both study
of crystal structure determination of compounds 4, 7 and their
electrochemical properties of compounds (4, 7, 9, 10, 12, 19) were
firstly investigated in this study.
Table 4
The hydrogen bond parameters for compounds 4 and 7.
D−H…A
D−H ( A˚ )
0.95(2)
H…A (A)
˚
D…A (A)
˚
< D−H…A (o)
S, S- and S, O-substituted-1,4-naphthoquinones (3, 4) and
Compound 4
C20-H14…C18
Compound 7
C11-H5…O2
C14-H14…C6
C4-H2…S2
(
12, 13) were synthesized from reactions of 2,3-dichloro-1,4-
2.66(1)i
3.61(1)
139.97(1)
naphthoquinone 1 with nucleopiles 2 or 11 according to gen-
eral method 1 (Scheme 1). Compound 2,3-bis(benzylsulfanyl)-1,4-
naphthoquinone 4 was crystallized from ethanol by slow evap-
oration as red block crystals. The solid-state molecular struc-
ture of 2,3-bis(benzylsulfanyl)-1,4-naphthoquinone 4 was deter-
mined by using X-ray single crystal diffractometer method. The
0.95(1)
0.95(2)
0.95(1)
2.69(1)ii
2.89(2)iii
2.99(2)iv
3.64(1)
3.84(1)
3.94(1)
161.30(1)
147.60(2)
128.98(1)
(
i) ½+x, 1.5−y, 2−z, (ii) -1+x, −y, −½+z, (iii) x, −y, ½+z, (iv) ½+x, −½+y, z

8
N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
Fig. 13. The hydrogen and intermolecular bonds of compound 4.
four compounds 7 [21], 8, 9 [16] and 10 [16] were synthesized
from one reaction of 1 with nucleophile 6 according to general
method 1 (Scheme 1). The black prisms single crystals of com-
pound 7 were determined by using X-ray single crystal diffrac-
tometer method. New mono S-coumarinyl ring substituted 1,4-
naphthoquinone compound 17 as a main target compound and
known 10 [16] as a side product were synthesized in the presence
of DMF and high temperature at 60°C according to general method
17, 19, 20), Voltammetric and in-situ UV-vis spectroelectrochem-
ical characterizations were performed in aprotic dimethyl sulfox-
ide (DMSO) solvent. It is reported in the literature that, while
the ideal redox response of NQ is two well-defined voltammetric
peaks, substituent environment and electrolyte type may alter the
redox mechanism of these species [25–29]. Therefore, more than
two sets of reduction couples could be observed due to the for-
mation of different dimeric species. It is very important to deter-
mine redox responses of newly synthesized NQ based functional
materials in order to decide their possible usage in different elec-
trochemical technologies. Especially determination of the dimeriza-
tion mechanism and, if it is possible, preventing dimerization is the
proposed route for these complexes. Therefore, here we reported
electrochemical mechanism of synthesized NQ compounds (3-4, 7-
10, 12-13, 15-17, 19-20). Redox parameters of all compounds de-
rived from the analyses of the CV and SWVs of the compounds
are listed in Table 1 for comparison. As shown in Table 1, the NQ
compounds studied here can be classified in two categories with
respect to their CV and SWV responses. The first category (3-4, 7-
8, 12-13, 15) which have S,S- and S,O-substituents, shows ideal two
sets of reduction couples. However, the second category (9-10, 16-
17, 19-20) which bear morpholinyl and/or coumarinyl substituents,
shows complication of two sets of reduction couples with the re-
dox waves of dimeric species.
2
(Scheme 2).
In this study, we used the technique of one-pot multicompo-
nent reactions to obtain the compounds 16 (in Scheme 1) and 20
in Scheme 2) containing substantial elements of all the reactants.
(
As shown in Schemes 1 and 2, starting compound 1 reacted in
a single reaction vessel with an equimolar amount of two nucle-
ophiles (6, 14) or (6, 18), respectively. These one-pot multicompo-
nent reactions occurred according to methods 1 and 3. Multicom-
ponent reactions are one-pot processes in which three or more
reactants come together in a single reaction vessel to give a fi-
nal product containing substantial elements for all the reactants.
Moreover, compounds 9 [16] and 15 in Scheme 1 and compound 19
[
23] in Scheme 2 were synthesized from these multicomponent re-
actions as side products. We have published previously some naph-
thoquinone derivatives which obtained by the one-pot multicom-
ponent processes [24].
CV and SWV responses of compounds 4, 7 and 12 are repre-
sented in Figs. 1–3 as examples for the compounds having two sets
of reduction couples. It is easily seen in these figures that while
the compounds of the first category (3-4, 7-8, 12-13, 15) generally
3
.2. Electrochemical studies
In order to investigate the redox mechanism of some 1,4-
naphthoquinone (NQ) derivatives (3, 4, 7, 8, 9, 10, 12, 13, 15, 16,

N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
9
Fig. 14. The hydrogen and intermolecular bonds of compound 7.
illustrate very similar reversible reduction couples, the substituent
environment of these compounds only alters the reversibility and
peak potentials of these redox processes. For instance, the com-
pound 4 (2,3-bis(benzylsulfanyl)-1,4-naphthoquinone) gives two
reduction couples at -0.43 V (ꢀEp = 67 mV and Ipa/Ipc = 1.00)
and -1.06 V (ꢀEp = 64 mV and Ipa/Ipc = 0.97) respectively. These
processes shift to -0.47 V (ꢀEp = 85 mV and Ipa/Ipc = 0.98) and
compounds give the following proposed mechanism for these com-
pounds:
NQ + e ↔ NQ•
–
–
•
–
–
2–
NQ
+ e ↔ NQ
NQ + NQ• ↔ NQ2•
–
–
-
1.16 V (ꢀEp = 70 mV and Ipa/Ipc = 0.97) for the compound 12
(
2,3-bis(isopropylsulfanyl)-1,4-naphthoquinone). Due to the pres-
•
–
–
2–
ence of oxy or sulfonyl bridge between 1,4-naphthoquinone and
the substituents, electronic structure of the substituents does
not significantly alter the redox activity and mechanism of 1,4-
naphthoquinone.
NQ2
+ e ↔ NQ2
Decreasing of the peak currents of the second reduction pro-
.−
.−
cesses are due to the conversion of NQ radical species to NQ2
Figs. 4–6 show CV and SWV responses of compounds 9, 15 and
.−
species and decreasing the concentration of NQ radical species
with this fast chemical reaction. When we compared the electro-
chemical responses of these compounds, we could conclude that
1
7 as examples for the second category (9-10, 16-17, 19-20) com-
pounds. The main differences between the CV responses of these
compounds from the compounds in the first category is the obser-
vation of a third reduction reaction at more negative potentials and
decreasing the peak currents of the second reduction couple with
respect to the peak current of the first reduction couple. These
different electrochemical responses most probably resulted from
.−
electron transfer abilities of the NQ, and NQ radical species could
be easily modulated by the electron-withdrawing or -donating
substituents of the electroactive NQ core. Therefore, the first re-
duction reactions of these compounds change from -0.20 V to -
0
.58 V by changing the substituents of the compounds. While
the formation of dimeric NQ2.
NQ22-
− radical and reduction of NQ2.−
to
the most easily reduced one is the compound 17 (2-(7-Sulphanyl-
4-methyl-coumarinyl)-3-chloro-1,4-naphthoquinone), the most diffi-
cultly reduced one is the compound 19 (2-Morpholinyl-3-chloro-1,4-
naphthoquinone). These data indicated that the electron releasing
species. It is well documented that dimeric NQ2.−
species
−
reduce at more negative potential than that of monomeric NQ.
radical species. Analysis of the CV and SWV responses of these

10
N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
compounds, which illustrate only the ideal two sets of reduction
reaction to monoanionic radical NQ.- and dianionic NQ
2−
.
The general trend of the spectral changes of the second cate-
gory compounds are similar to those of the first category com-
pounds. However, during the second reduction reaction, a split
new band is observed as shown in Figs. 9 and 10. For example,
the compound 12 shows new bands at 403 and 430 nm after the
second reduction reaction as shown in Fig. 9. The band at 403
nm may be assigned to the dimeric NQ .- and the band at 430
2
nm could be assigned to dianionic NQ 2 species. The compound
−
9
gives very similar spectral changes for the formation of dimeric
NQ .- and monoanionic NQ.- radicals (Fig. 10). The bands at 400
2
and 432 nm observed after the second reduction reaction charac-
terize the formation of dimeric NQ .- and dianionic NQ
−2
species
2
for the compound 9. Moreover, isosbestic points recorded during
the second reduction reaction oscillate continuously. These spectral
changes illustrate presence of two different redox species in the
media. These species may be dimeric NQ .- and dianionic NQ
2−
.
2
These spectral changes support the electrochemical responses of
the second category compounds, which give redox responses of
dimeric in addition to the monomeric NQ species.
3
.3. X-ray study
The compounds 2,3-bis(benzylsulfanyl)-1,4-naphthoquinone 4
and 2,3-bis(ethylsulfanyl)-1,4-naphthoquinone 7 crystallized in the
orthorhombic and monoclinic, space groups P2 2 2 and Cc with
1
1 1
Z = 4 from ethanol as red block and black prisms, respectively.
Displacement ellipsoids are plotted at the 50% probability level in
Figs. 11 and 12. The crystal data and refinement parameters for
compounds 4 and 7 were summarized in Table 2. The selected
Fig. 15. Unit cell packing diagrams of the compounds 4 (A) and 7 (B).
˚
bond distances (A), bond and torsion angels (°) for compounds 4
and 7 were listed in Table 3.
The double bonds length of the quinone moiety agreed well
with corresponding distance in a similar compound [16,24]. The
bond lengths of C1-O1/C4-O2 of compound 4 and C10-O2/C7-O1
groups cause to the shifting of the reduction processes towards
more negative potentials. Morpholinyl group on compound 19 be-
have the most like electron releasing group and the substituents of
the compound 17 behave the most like electron withdrawing group
among the compounds studied here.
˚
of compound 7 were 1.215(9)/1.222(9) and 1.290(1)/1.170(1) A, re-
spectively, typical of C=O bonds. C-C-C and C-C-O angles were very
close to 120°, as expected for sp2 hybridized atoms in the com-
pounds 4 and 7. In the compound 7, the both rings of naphtho-
quinone unit were planar with a maximum deviations of 0.0115(1)
In-situ UV-Vis spectroelectrochemical studies were carried out
to perform assignments of the redox reactions and to determine
the spectra of the electrogenerated species of the compounds. Al-
though in-situ FT-IR spectroelectrochemical studies of these type
compounds were frequently reported in the literature, this is the
first study for the in-situ UV-Vis spectroelectrochemical studies of
NQ compounds in the literature [30–32]. There is only one pa-
per in the literature, which reports the spectra of the neutral,
monoanionic and dianionic NQ species [33]. However, we repre-
sented spectral changes recorded during the reduction reactions in
order to clarify the redox reactions and demonstrate optical re-
sponses of the redox species of NQ compounds. The initial spec-
tra of all compounds are similar to each other, spectral changes
during the reduction reactions of the first and second categories.
Figs. 7 and 8 show in-situ UV-Vis spectral changes during the re-
duction reactions of compounds 4 and 15 as examples of the first
category compounds. For example, for the compound 4 under open
circuit potential, the compound gives a band at 466 nm due to the
˚
˚
A (plane 1 = C1-C2-C3-C4-C5-C6) and 0.0340(1) A (plane 2 = C1-
C7-C8-C9-C10-C2). Dihedral angle was 2.342(1)° between planes 1
and 2. In solid state the ethylsulphanyl group of the molecule is
non planar with respect to the quinone ring. Unit cell packing dia-
grams for compounds 4 and 7 were drawn in Figs. 14 and 15. The
whole packing diagrams exhibited a zigzag-shaped intermolecular
chain along the b axis in the unit cells. The hydrogen bond dis-
tances and angles of compounds 4 and 7 were given in Table 4. An-
other intermolecular bond for compound 4 between C1-O2 had the
following parameters; C4-O2…C1(i): 3.19(1)A, 104.63(1)°, (i) −1+x,
y, z, (Fig. 13).
˚
4. Conclusion
The heteroatom substituted-1,4-naphthoquinone derivatives (3,
4, 7, 8, 9, 10, 12, 13, 15, 16, 17, 19 and 20) were synthesized acour-
ding to method 1-3 and their structures were characterized by us-
ing micro analysis, UV-Vis, 1H-, 13C NMR and MS in this study.
The six known 1,4-naphthoquinone compounds (4, 7, 9, 10, 12,
19) were yielded from these reactions. The synthesis method and
spectral characterizations of these known quinone compounds 4,
7, 9, 10, 12 and 19 were previously reported in the related lit-
erature [16,21–23]. Altough these compounds (4, 7, 9, 10, 12, 19)
were not new, the study of crystal structure determination of com-
pounds 4, 7 and their electrochemical properties of compounds
∗
π to π electronic transition (Fig. 7). During the first reduction
reaction, the bands at 466 nm increase in absorption with shift-
ing to the longer wavelengths (521 nm). During the second reduc-
tion reaction, while the band at 521 nm decreases in intensity, a
new band is observed at 443 nm. Observation of the well resolved
isosbestic points (at 368 nm during the first reduction and at 358
nm during the second reduction reaction) illustrate formation of
one type reduced species during these processes. These spectral
changes support the electrochemical responses of the first category

N.G. Deniz, C. Sayil and D. Akyüz et al. / Journal of Molecular Structure 1224 (2021) 129145
11
were firstly investigated in this study. Crystal structures of 2,3-
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[
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groups of the NQ derivatives significantly alters the redox mech-
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tives is strongly influenced by the chemical propertied of the ring
substituents. When the NQ bearing morpholinyl and/or coumarinyl
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(
3, 4, 7, 8, 12, 13, 15) showed ideal two sets of reduction couples.
0
36.
Morpholinyl and/or coumarinyl moieties also alters the redox po-
tentials significantly. In-situ UV-Vis spectroelectrochemical analyses
of NQs supported the proposed redox mechanism.
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Declaration of Competing Interest
[
17] A. Altomare, G. Cascarano, C. Giacovazzo, A. Guagliardi, M. Burla, G. Polidori,
M. Camalli, J. Appl. Crystalogr. 27 (1994) 435, doi:10.1107/S002188989400021X.
18] D.J. Watkin, C.K. Prout, J.R. Carruthers, J.R. Betteridge, Crystals, Issue10, Chem-
ical Crystallography Laboratory, Oxford University, Oxford, 1998.
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared to
influence the work reported in this paper.
[
[
19] L.J. Farrugia, J. Appl. Cryst. 30 (1997) 565, doi:10.1107/S0021889897003117.
[
20] Crystallographic data (excluding structure factors) for the structure in this
paper has been deposited in the Cambridge Crystallographic Data Centre as
supplementary publication number CCDC-1041226, 1041225 for compounds4
and7. Copies of the data can be obtained, free of charge, via www.ccdc.cam.ac.
uk/conts/retrieving.html or from the Cambridge Crystallographic Data Centre,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033. E-mail:
deposit@ccdc.cam.ac.uk .
CRediT authorship contribution statement
Nahide Gulsah Deniz: Supervision, Visualization, Writing - re-
view & editing. Cigdem Sayil: Methodology, Writing - original
draft. Duygu Akyüz: Formal analysis. Atif Koca: Investigation,
Methodology, Formal analysis.
[
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Acknowledgements
We gratefully thank the Research Fund of Istanbul University-
Cerrahpasa for financial support of this work (Project Numbers:
FBA-2019-30472, FBA-2019-32783, 36017).
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